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335353 Specification of Letters Patent.

No Drawing.

To all whom it may concern."

Be it known that 1, JAMES H. STEBBINS, J12, a citizen of the UnitedStates, residing at N o. 80 Madison avenue, in the city, and State ofNew York, have invented cer tain new and useful Improvements inDyestuffs; and I do hereby declare the following to be a full, clear,and exact description of the invention, such as will enable othersskilled in the art to which it appertains tomake and use the-same.

This invention relates to new azo dyestuffs and methods of producing thesame; and more particularly to azo dyestufi's soluble in water andcapable of dyeing both wool and cotton without theuse of mordants.

The new dyestufi's of the present invention-are derived from1.8-dioxynaphthalenewhere R is the necleus of the chromotropic acid, Rthe diaryl nucleus of benzidin or its equivalent, it an aromatic nucleusof an end component such as a naphtholsulfonic acid, and R an aromaticnucleus derived from a diazotized aromatic amin such as those referredto above. These dyestuffs are blue to black to brown products soluble inwater and capable of dyeing cotton in sodium sulfate baths bluish orpurplish shades, and also capable of dyeing wool in acid sodium sulfatebaths blue to black to brown shades.

In the production of the chromotropic acid is combined with county, I

Patented July 31,1931? Application filed January 9, 1917. Serial No.141,361.

tetrazotized benzidin or its equivalent and also with a diazotizedaromatic amin such 9 as those referred to above; and the tetrazotizedbenzidin is also combined with an end component such as1.5-naphtholsulfonic acid or lA-naphtholsulfonic acid The invention willbe further illustrated b V. the following specific examples. In theseexamples, I will refer to the l.8-dioXynaphthalene-35- disulfonic acidby its simpler name chromotropic acid. This chromotropic acid has thefollowing graphically represented constitution, as is indicated by thename 1.8-dioxynaphthalene-3.6-disulfonic"acid.

| lW nso sosn Example 1213.8 kgs. of para-nitranilin are diazotized inthe usual way by treatment with liters of hydrochloric acid of 1.2specific gravity diluted with 200 liters of water and 6.9 kgs. sodiumnitrite dissolved in 200 liters of water. para-nitranilin chloridsolution thus .obtained is then gradually stirred into a solution of40.4: kgs. of the sodium salt of chromotropic acid in. 100 liters ofwater. At the-end of the operation, it will be found that the solutionhas a strong acidreaction. 1

A strong scarlet dyestud is thusobtained. 'The dye solution is allowedto stand over night. It is then made alkaline by the addition of 140.0kgs. anhydrous sodium carbonate which is sufficient to neutralize the 60liters of hydrochloric acid previously and in the accompanying claims,

The diazo- I used and 37 .5 liters of hydrochloric acid to u be used inthe next operation. A dark blue precipitate With apurplish solution isformed. On heating to boiling the precipitate is dissolved yielding anintensely purple solution. On cooling the dyestufl' separates in theform of its sodium salt, as a semisolid mass of crystals. Thecrystalline mass is then broken up by stirring and treated underconstant stirring with one molecular proportion of tetrazo-diphenylchlorid. The solution immediately turns black with the formation of ablack precipitate of the new intermediate product. The mixture isallowed to stand in the cold for about 6 hours and there is then stirredinto the same a solution of 224 kgs. of 1.5-naphtholsulfonic aciddissolved in 300 liters of water and the whole is made alkaline with 113kgs. of canstic soda. The black precipitate of the intermediate beginsto 'dissolve immediately, yielding a violet-colored solution but onstanding, .it is ultimately, transformed into a violet-black precipitatewith only a small amount of coloring matter in solution. The precipitateis filtered off and dried.

The new azo dyestuif thus produced dissolves in hot'water with a bluishBordeaux color. 011 cooling itpartly separates out again. It dyesu'mnordanted cotton in a neutral sodium sulfate bath a bluish shade;while silk and wool are dyed in an acid bath of sodium sulfate variousshades of brown to black, depending upon the quantity of dye used.

The tetrazo-diphenyl chlorid referred to in the above example may beprepared from benzidin as follows:

18.4: kgs. benzidin are dissolved in 37.3 liters of hydrochloric acid of1.2 specific gravity and 300 liters of water. The solution is cooledwith ice and diazotized by treatment with 13.8 lags. sodium nitritedissolved in 300 liters of water.

Example 2: 10 kgs. of para-amido-phenylglycin (obtained by the action ofmonochloracetic acid upon paraphenylenediamin) are dissolved in litersof hydrochloric'acid of 1.2 specific gravity diluted with 1000 liters ofwater. The solution is now cooled with ice and diazotized by treatmentwith i kgs. sodium nitrite dissolved in 100 liters of water. Thediazophenylglycin chlorid solution is then stirred into a solution of 24kgs. of the sodium salt of chromotropic acid, kgs. sodium carbonate and500 liters of water. In this case, it was found more ad v antageous tooperate in an alkaline solunon.

thus formed. The crimson dye solution is then treated with 30 kgs. moreof sodium carbonate and then with one molecular pro portion oftetrazo-diphenyl chlorid. A voluminous brown precipitate of a newintermediate is formed. The latter is allowed to stand forseveral hourswith occasional stir ring and is then stirred into a solution of 13 kgs.of Li-naphtholsulfonic acid in 500 An intense very soluble crimson dyeany remaining precipitate and to forma bath a bluish purple'color; whilewool is dyed in an acid sodium sulfate bath a plum to almost blackcolor, depending upon the quantity of dye used.

The tetrazo-diphenyl chlorid used in this example can be prepared bydissolving 11 kgs of benzidin in 22 liters hydrochloric acid of 1.2specific gravity diluted With 1000 liters of water and by diazotizingwith 8.3 kgs. sodium nitrite dissolved in 50 liters of water.

Example 3; 18.4 kgs. benzidin are converted into tetrazo-diphenylchlorid in the usual manner with 22 liters of hydrochloric acid of 1.2specific gravity, 1000 liters of water and 7.5 kgs. sodium nitrite; andthe resulting product is then stirred into a solution of 22 kgs. of thesodium salt of chromotropic acid in 500 liters'of Water containing 30kgs. of sodium carbonate. A purplish precipitate of a primaryintermediate compound is thus formed. It is allowed tostand in the'coldfor a few hours with frequent stirring and there is then added to it 20kgs. more of sodium carbonate and the latter is stirred untildissolved.The solution of the primary intermediate compound is then treated withconstant stirring with one molecular proportion of diazo-picramic acid.The solution turns reddish-brown, and a dark brown to black precipitateof a secondary intermediate compound is formed. This is allowed to standwith occasional stirring for several hours and is then treated withconstant stirring with 12 kgs. of the 1.4 naphtholsulfonic acid, 500liters of water and 30 kgs. of sodium carbonate. The solution now beginsto turn purple and in a comparatively short time it assumes an intenseviolet color while the precipitate of the secondary intermediate productgoes into solution. On being allowed to stand over night, it will befound that the new dye-stufi has for the most part separated as a"semi-crystalline black to dark brown precipitate. This precipitatedsdissolved on heating to boiling and is re-prec1p1tated as the sodiumsalt by means of sodium chlorid; and the precipitate is filtered off anddried.

The product thus obtained is a very dark,

almost black product which is quite easily soluble in water.

The yield is very good. The product dyes cotton in a sodium sulfate batha purplish blue shade; It dyes wool .in an'acid sodium sulfate bath aplum to the quantity 3.7 kgs. sodium gradually stirred in. A clearsolution of ,ther be diazo-picramic acid is thus obtained which isallowed to stand untilcomplete absorption of all the nitrous acid.

In place of the-IA-naphtholsulfomc acid used in the above example, othersuitable end components can be used.

It will be noted that the dyestuffs described in' the specific examplesare derived from chromotropic acid and contain thenucleus of this acidas one of the intermediate nuclei. It will further be noted that theother intermediate nucleus is a diaryl nucleus such as that of benzidin.It will furnoted that the tetrazotized benzidin or the tetrazoiphenylchlorid is coupled or combined witl fitfihe chromotropic acid and withanother co pling agent which forms an end component of the dyestufi. Thechromotropic acid is also combined with another diazotized aromaticamin,*the nucleus of which forms the other end nucleus or end componentof the dyestufi'.

-\ While I have illustrated and described certain specific dyestufls andgiven specific examples of their production, I do not wish to limitmyselfthereto as variations and subas the substitution of certainequivalents; but what I claim as my invention is as follows;

.1. As new products, azo dyestuffs of the following graphicallyrepresented consti tutionf in which R, is the nucleus of1.8-dioxynaphthalene-3.6-disulfonic acid, R the diphenyl nucleus, R thenucleus of a naphthol sulfonic acid and R an aromatic nucleus, saiddyestuffs being blue to black to brown products soluble in water, dyeingcotton in sodium sulfate baths bluish or purplish shades, and dyeingwool in acid sodium sulfiatebaths blue to black to brown shades;substantially as described. I

2. As new products, azo dyestuffs of the of strong aqua-ammonia anddiluted shades, and dyeing following graphically representedconstitution:

R-N N R N i N R N NR in which R, is the nucleus ofLS-dioxyiiaphthalene-3.6-disulfonicacid, R a diaryl nucleus, R thenucleus of a naphthol sulfonic acid, and R a substituted benzenenucleus,

- said dyestuffs being blue to black to brown products soluble in water,dyeing cotton. in sodium sulfate baths bluish or purplish shades, anddyeing wool in substantially as described.

As new products, azo dyestuffs of the following graphically representedconstitu-' tion thalene-3.6- disulfonic acid, R a diaryl nuacid sodiumsul- 'fate baths blue to black to brown shades;

cleus, R, an aromatic nucleus and R the nucleus of picramic acid, saiddyestufis being blue to black to brown products soluble in water, dyeingcotton in sodium sulfate bath bluish or purplish shades, and dyeing woolin acid sodium to brown shades; substantially asdescribed. I 4. Asa newproduct, the azo dyestuif of the following graphically representedconstitution: v

R-N N"R -N: N-R N: N-R

in which R, is the thalene-3.6-disulfonic acid, R the diphenyl nucleus,R the nucleus of 1.4 naphtholsulfonic acid and R the nucleus of picramicacid, said dyestufi being a dark almost black product easily soluble inwater, dyeing cot ton in sodium sulfate baths purplish blue' wool inacid sulfateof soda baths plum to black shades; substantially asdescribed.

- 5. The method of producing azo dyestuffs,

sulfate baths blue to black,

nucleus of 1.8-dioxynaph soluble in water and dyeing both wool andcotton, which comprises combining 1.8-dioxynaphthalene-3.6-disulfonicacid with a diazotized aromatic amin and with tetra'zotized benzidin,and combining with the tetrazotized benzidin also a naphthol sulfonicacid; substantially as described; i

6. The method of producing azo dyestuffs soluble in water and dyeingboth wool and cotton,which comprises combining1.8-dioxynaphthalene-3.6-disulfonic acid with a diazotized anllincontaining an acid group and with tetrazotizedbenzidin', and combiningwith theitetrazotized benzidin also a naphthol sulfonicacidysubstantial'ly as described. 1 t

'7: The method .of producin azo dyestufi's soluble in Water and dyeincotton, which comprises com naphthalene-3.6,-disulfonic ining1;8-dioxyacid with diazo- 0th wool and sized picramic acid and Withtetrazotized benzidin, and combining with the tetrazotized benzidin alsoan aromatic nucleus; substantially as described.

8. The method of producing an azo dyestuff soluble in Water and dyeingsilk, W001 and cotton, which comprises combining 1.8 dicxynaphthaiene3.6 disulfonic acid first with tetrazotized benzidin and then withdiazotized picrainic acid, and combining the 10 intennediate productthus obtained with 1A naphthol sulfonic acid; substantially asdescribed. v

In testimony whereof I aifix my signature.

JAMES H. STEBBINS, JR.

e2 aids gatent may be cbtained for me cents each, by addressing the"Commissioner 1 Patent Washinfitn, D. G.

